Bis(2,6-dichloro­benz­yl)selane

Zhou, M.-Y.; Li, Y.-Q.; Zheng, W.-J.

doi:10.1107/S1600536812008318

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o921

doi:10.1107/S1600536812008318

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Bis(2,6-dichlorobenzyl)selane

Mei-Yun Zhou,^a Yi-Qun Li ^a and Wen-Jie Zheng ^a ^*

^aDepartment of Chemistry, Jinan University, Guangzhou 510632, People's Republic of China
^*Correspondence e-mail: tzhoumy@jnu.edu.cn

(Received 11 February 2012; accepted 24 February 2012; online 29 February 2012)

The title molecule, C₁₄H₁₀Cl₄Se, features a selenide bridge between two dichlorobenzyl units. The dihedral angle between the two benzene rings is 107.9 (16)°. In the crystal, weak π–π face-to-face aromatic interactions are observed [centroid–centroid distance between two adjacent (but crystallographically different) phenyl rings = 3.885 (5) Å], providing some packing stability. Short Cl⋯Cl contacts of 3.41 (2) Å are observed.

Related literature

For applications of organoselenium compounds, see: Dinesh et al. (2007 ). For related structures, see: Fabiano et al. (2005 ); Fuller et al. (2010 ).

Experimental

Crystal data

C₁₄H₁₀Cl₄Se
M_r = 398.98
Monoclinic, P 2₁ /n
a = 8.1144 (5) Å
b = 12.2250 (5) Å
c = 15.3505 (9) Å
β = 102.479 (6)°
V = 1486.78 (14) Å³
Z = 4
Mo Kα radiation
μ = 3.23 mm⁻¹
T = 293 K
0.1 × 0.1 × 0.04 mm

Data collection

Agilent Xcalibur Sapphire3 Gemini ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ) T_min = 0.659, T_max = 1.000
5405 measured reflections
2628 independent reflections
1902 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.127
S = 1.04
2628 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 1.19 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812008318/nk2146sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008318/nk2146Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812008318/nk2146Isup3.cml

checkCIF report

Comment top

The interest in the chemistry of organoselenium compounds has increased remarkably in the last few decades due to their synthetic applications and biological activities(Dinesh et al.,2007). The title molecule, features a selenide bridge between two Dichlorobenzyl units. The dihedral angle between the two benzene rings is 107.9 (16)°. In the crystal, weak π–π intermolecular face-to-face aromatic interactions are observed [centroid-centroid distance between 6-Membered ring (C₂, C₃, C₄, C₅, C₆, C₇) and 6-Membered ring (C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄) = 3.885 (5) Å], providing some packing stability. Short Cl···Cl contacts of 3.41 (2) Å between Cl2 and Cl3 of adjacent molecules are also observed.

Related literature top

For applications of organoselenium compounds, see: Dinesh et al. (2007). For related structures, see: Fabiano et al. (2005); Fuller et al. (2010).

Experimental top

A solid mixture of sodium borohydride (0.38 g, 10 mmol) and elemental selenium (0.40 g, 5 mmol) is stirred in a two naked flask under argon and maintained at 20 °C using a water bath. Dropwise addition of anhydrous EtOH (1.40 g, 30 mmol) to this mixture favours the rapid evolvement of hydrogenand produces a white-grey solid. Addition of anhydrous DMF (10 mL) produces a red-brown solution, which slowly leads to a colourless one. 2,6-Dichlorobenzylchloride (10 mmol) is added dropwise to the solution of solution reported above. The resulting milky medium was stirred before hydrolysis and extraction with Et₂O. The obtained organic layer was dried over MgSO₄ overnight. The organic residue was further purified by silica gel column using dichloromethane as eluent, The solvent was evaporated and the solid residue was recrystallized from CH₃Cl to give the product as yellow crystals (yield: 1.62 g, 80.5%).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability.

Bis(2,6-dichlorobenzyl)selane top

Crystal data top

C₁₄H₁₀Cl₄Se	F(000) = 784
M_r = 398.98	D_x = 1.782 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.7107 Å
a = 8.1144 (5) Å	Cell parameters from 1490 reflections
b = 12.2250 (5) Å	θ = 3.1–29.2°
c = 15.3505 (9) Å	µ = 3.23 mm⁻¹
β = 102.479 (6)°	T = 293 K
V = 1486.78 (14) Å³	Plate, metallic pale yellow
Z = 4	0.1 × 0.1 × 0.04 mm

Data collection top

Agilent Xcalibur Sapphire3 Gemini ultra diffractometer	2628 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1902 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 16.0288 pixels mm^-1	θ_max = 25.0°, θ_min = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −11→14
T_min = 0.659, T_max = 1.000	l = −10→18
5405 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.060P)²] where P = (F_o² + 2F_c²)/3
2628 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 1.19 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₁₄H₁₀Cl₄Se	V = 1486.78 (14) Å³
M_r = 398.98	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.1144 (5) Å	µ = 3.23 mm⁻¹
b = 12.2250 (5) Å	T = 293 K
c = 15.3505 (9) Å	0.1 × 0.1 × 0.04 mm
β = 102.479 (6)°

Data collection top

Agilent Xcalibur Sapphire3 Gemini ultra diffractometer	2628 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	1902 reflections with I > 2σ(I)
T_min = 0.659, T_max = 1.000	R_int = 0.031
5405 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.04	Δρ_max = 1.19 e Å⁻³
2628 reflections	Δρ_min = −0.50 e Å⁻³
172 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Se1	0.89325 (7)	0.75838 (4)	0.18239 (3)	0.0556 (2)
Cl3	0.52156 (18)	0.76390 (11)	−0.06014 (11)	0.0679 (4)
Cl4	0.8752 (2)	1.05598 (11)	0.17334 (10)	0.0772 (5)
Cl2	0.66481 (17)	0.48664 (13)	0.09733 (12)	0.0758 (5)
Cl1	1.29563 (18)	0.64440 (12)	0.12621 (12)	0.0768 (5)
C9	0.7067 (6)	0.9115 (3)	0.0528 (3)	0.0394 (11)
C3	1.1568 (6)	0.5365 (4)	0.1322 (3)	0.0440 (11)
C2	0.9848 (6)	0.5574 (3)	0.1111 (3)	0.0379 (10)
C1	0.9110 (6)	0.6662 (3)	0.0799 (3)	0.0445 (12)
H1A	0.7999	0.6561	0.0419	0.053*
H1B	0.9818	0.7021	0.0452	0.053*
C14	0.7921 (7)	1.0097 (4)	0.0657 (3)	0.0487 (12)
C8	0.6873 (6)	0.8404 (4)	0.1287 (3)	0.0494 (12)
H8A	0.5964	0.7888	0.1079	0.059*
H8B	0.6552	0.8855	0.1743	0.059*
C7	0.8824 (6)	0.4681 (4)	0.1202 (3)	0.0433 (11)
C6	0.9468 (7)	0.3671 (4)	0.1470 (3)	0.0539 (14)
H6	0.8745	0.3094	0.1519	0.065*
C10	0.6395 (6)	0.8837 (4)	−0.0359 (3)	0.0432 (11)
C5	1.1186 (8)	0.3511 (4)	0.1669 (4)	0.0593 (15)
H5	1.1627	0.2824	0.1846	0.071*
C11	0.6591 (7)	0.9485 (5)	−0.1069 (4)	0.0605 (14)
H11	0.6120	0.9276	−0.1652	0.073*
C13	0.8124 (8)	1.0760 (4)	−0.0042 (4)	0.0653 (16)
H13	0.8693	1.1422	0.0071	0.078*
C12	0.7480 (8)	1.0431 (5)	−0.0901 (4)	0.0700 (17)
H12	0.7654	1.0860	−0.1373	0.084*
C4	1.2247 (7)	0.4366 (4)	0.1604 (3)	0.0543 (14)
H4	1.3411	0.4269	0.1750	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Se1	0.0778 (5)	0.0396 (3)	0.0418 (3)	0.0097 (2)	−0.0041 (3)	0.0019 (2)
Cl3	0.0577 (9)	0.0589 (8)	0.0758 (10)	−0.0002 (6)	−0.0104 (7)	−0.0111 (7)
Cl4	0.1139 (14)	0.0446 (8)	0.0628 (10)	0.0014 (8)	−0.0035 (9)	−0.0108 (7)
Cl2	0.0427 (8)	0.0789 (10)	0.1042 (13)	−0.0092 (7)	0.0122 (8)	−0.0189 (9)
Cl1	0.0533 (9)	0.0711 (10)	0.1094 (13)	−0.0159 (7)	0.0250 (9)	0.0003 (9)
C9	0.044 (3)	0.031 (2)	0.044 (3)	0.015 (2)	0.014 (2)	0.006 (2)
C3	0.045 (3)	0.046 (3)	0.042 (3)	−0.003 (2)	0.011 (2)	−0.004 (2)
C2	0.039 (3)	0.042 (2)	0.030 (2)	0.000 (2)	0.004 (2)	−0.004 (2)
C1	0.049 (3)	0.043 (3)	0.039 (3)	0.002 (2)	0.006 (2)	0.010 (2)
C14	0.062 (3)	0.035 (3)	0.048 (3)	0.006 (2)	0.011 (3)	−0.001 (2)
C8	0.056 (3)	0.054 (3)	0.042 (3)	0.002 (2)	0.020 (2)	0.004 (2)
C7	0.038 (3)	0.046 (3)	0.045 (3)	−0.004 (2)	0.006 (2)	−0.010 (2)
C6	0.077 (4)	0.032 (3)	0.056 (3)	−0.008 (3)	0.021 (3)	−0.005 (2)
C10	0.041 (3)	0.042 (3)	0.045 (3)	0.007 (2)	0.005 (2)	0.000 (2)
C5	0.081 (4)	0.041 (3)	0.054 (3)	0.018 (3)	0.010 (3)	0.004 (2)
C11	0.067 (4)	0.068 (4)	0.044 (3)	0.023 (3)	0.007 (3)	0.003 (3)
C13	0.089 (5)	0.039 (3)	0.071 (4)	0.003 (3)	0.023 (3)	0.015 (3)
C12	0.090 (5)	0.065 (4)	0.062 (4)	0.013 (3)	0.032 (3)	0.027 (3)
C4	0.053 (3)	0.055 (3)	0.051 (3)	0.018 (3)	0.003 (3)	−0.006 (3)

Geometric parameters (Å, º) top

Se1—C1	1.965 (4)	C14—C13	1.382 (7)
Se1—C8	1.970 (5)	C8—H8A	0.9700
Cl3—C10	1.745 (5)	C8—H8B	0.9700
Cl4—C14	1.738 (5)	C7—C6	1.369 (7)
Cl2—C7	1.739 (5)	C6—H6	0.9300
Cl1—C3	1.749 (5)	C6—C5	1.375 (7)
C9—C14	1.379 (6)	C10—C11	1.385 (7)
C9—C8	1.490 (6)	C5—H5	0.9300
C9—C10	1.395 (6)	C5—C4	1.372 (7)
C3—C2	1.387 (6)	C11—H11	0.9300
C3—C4	1.371 (6)	C11—C12	1.359 (8)
C2—C1	1.494 (6)	C13—H13	0.9300
C2—C7	1.397 (6)	C13—C12	1.370 (8)
C1—H1A	0.9700	C12—H12	0.9300
C1—H1B	0.9700	C4—H4	0.9300

C1—Se1—C8	99.2 (2)	C2—C7—Cl2	118.5 (4)
C14—C9—C8	122.0 (4)	C6—C7—Cl2	118.9 (4)
C14—C9—C10	115.5 (4)	C6—C7—C2	122.6 (5)
C10—C9—C8	122.4 (4)	C7—C6—H6	120.1
C2—C3—Cl1	118.4 (4)	C7—C6—C5	119.8 (5)
C4—C3—Cl1	118.0 (4)	C5—C6—H6	120.1
C4—C3—C2	123.6 (5)	C9—C10—Cl3	119.6 (4)
C3—C2—C1	123.5 (4)	C11—C10—Cl3	117.6 (4)
C3—C2—C7	115.0 (4)	C11—C10—C9	122.8 (5)
C7—C2—C1	121.5 (4)	C6—C5—H5	120.1
Se1—C1—H1A	109.6	C4—C5—C6	119.9 (5)
Se1—C1—H1B	109.6	C4—C5—H5	120.1
C2—C1—Se1	110.3 (3)	C10—C11—H11	120.5
C2—C1—H1A	109.6	C12—C11—C10	119.0 (5)
C2—C1—H1B	109.6	C12—C11—H11	120.5
H1A—C1—H1B	108.1	C14—C13—H13	120.3
C9—C14—Cl4	120.0 (4)	C12—C13—C14	119.4 (5)
C9—C14—C13	122.6 (5)	C12—C13—H13	120.3
C13—C14—Cl4	117.4 (4)	C11—C12—C13	120.6 (5)
Se1—C8—H8A	108.8	C11—C12—H12	119.7
Se1—C8—H8B	108.8	C13—C12—H12	119.7
C9—C8—Se1	113.6 (3)	C3—C4—C5	119.1 (5)
C9—C8—H8A	108.8	C3—C4—H4	120.5
C9—C8—H8B	108.8	C5—C4—H4	120.5
H8A—C8—H8B	107.7

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀Cl₄Se
M_r	398.98
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.1144 (5), 12.2250 (5), 15.3505 (9)
β (°)	102.479 (6)
V (Å³)	1486.78 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.23
Crystal size (mm)	0.1 × 0.1 × 0.04

Data collection
Diffractometer	Agilent Xcalibur Sapphire3 Gemini ultra diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.659, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5405, 2628, 1902
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.127, 1.04
No. of reflections	2628
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.19, −0.50

Computer programs: CrysAlis PRO (Agilent, 2010), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Acknowledgements

This work was supported by grants from the National Natural Science Fund (grant Nos. 31000816, 21071062).

References

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